Reactive azo dyes, method for the production and use thereof

ABSTRACT

The present invention relates to reactive dyes of the general formula (1) 
                 
 
where X 1 , X 2 , R, M, m and n are each as defined in claim 1, processes for their preparation and also their use for dyeing and printing hydroxyl- and/or carboxamido-containing materials.

RELATED APPLICATIONS

This application is a 371 application of PCT/EP02/13410 filed on Nov.28, 2002 and claims benefit to German application no. 101 59 001.6 filedNov. 30, 2001.

The present invention relates to the field of fiber-reactive dyes.

DE-A-4434989, DE 19600765, DE 19810906 and EP-A 922735 disclose dyeswhich are structurally similar to the hereinbelow described dyes of thepresent invention, but which differ with regard to the reactive group orin the type of coupling component. These known dyes have a number oftechnical disadvantages in the dyeing of textile materials.

It is an object of the present invention to ameliorate these technicaldisadvantages.

It has now been found that, surprisingly, the hereinbelow described dyesof the general formula (1) are advantageous over the known dyes:

The present invention accordingly provides reactive dyes of the generalformula (1)

where

-   -   R is hydrogen, alkyl or substituted alkyl    -   X¹ is halogen, amino, optionally substituted amino or X²,    -   X² is a substituent of the general formula (2)        where    -   R¹ is substituted or unsubstituted aryl,    -   B is alkylene which may be interrupted by an oxygen atom, and    -   R² is a —SO₂CH═CH₂ or —SO₂CH₂CH₂Z radical, where Z is a moiety        which can be eliminated by the action of alkali,    -   n and m are each 0 or 1, and    -   M is hydrogen, ammonium, an alkali metal or the equivalent of an        alkaline earth metal.

In the general formula (1), an alkali metal M can be in particularlithium, sodium and potassium, whereas the alkaline earth metal iscalcium in particular. Preferably, M is hydrogen or sodium.

Halogen X¹ is in particular fluorine or chlorine, and substituted aminodenotes in particular amino which is substituted by an aryl radicalbearing one or more fiber-reactive radicals —SO₂CH═CH₂ or —SO₂CH₂CH₂Z′,where Z′ represents a moiety which can be eliminated by the action ofalkali. Preferably, amino is substituted by m-sulfatoethylsulfonylphenylor p-sulfatoethylsulfonylphenyl.

Alkyl R is preferably (C₁-C₈)-alkyl and particularly preferably(C₁-C₄)-alkyl. Examples of alkyl groups of this type are methyl, ethyl,n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl and tert-butyl. Alkyl Rcan be substituted by an SO₃H group for example.

Aryl R¹ is in particular phenyl which can be mono- or polysubstituted byfor example (C₁-C₄)-alkyl, (C₁-C₄)-alkoxy, chlorine, fluorine or SO₃H.Preferably, R¹ is phenyl or an aryl radical which bears a sulfo group.

Alkylene B is preferably (C₁-C₈)-alkylene and particularly preferably(C₁-C₄)-alkylene. Examples of alkylene groups of this type aremethylene, ethylene, n-propylene, i-propylene and butylene. Alkyleneinterrupted by an oxygen atom is preferably —(CH₂)₂—O—(CH₂)₂—.

Examples of Z radicals which can be eliminated by the action of alkali,ie under dyeing conditions, are chlorine, bromine, sulfato, thiosulfato,phosphate, (C₂-C₅)— alkanoyloxy such as for example acetyloxy,benzoyloxy, sulfobenzoyloxy or p-toluylsulfonyloxy, of which sulfato ispreferred.

The groups “sulfato”, “thiosulfato” and “phosphate” include not onlytheir acid form but also their salt form. Accordingly, thiosulfatogroups conform to the general formula —S—SO₃M, phosphato groups conformto the general formula —OPO₃M₂ and sulfato groups conform to the generalformula —OSO₃M, in each of which M is as defined above.

Preferred reactive dyes of the present invention are those of thegeneral formula (1) where the radical of the general formula (2)corresponds to one of the radicals (2-1) to (2-4)

where M is as defined above.

Particular preference is given to the dyes of the formulae (1a) to (1c)according to the invention

where M, n and X¹ are each as defined above.

The reactive dyes of the general formula (1) according to the inventionare generally present as a preparation in solid or liquid (dissolved)form. In solid form, they generally contain the electrolyte saltscustomary in the case of water-soluble and especially fiber-reactivedyes, such as sodium chloride, potassium chloride and sodium sulfate,and can further contain the auxiliaries customary in commercial dyes,such as buffer substances capable of setting a pH in aqueous solutionbetween 3 and 7, such as sodium acetate, sodium borate, sodiumbicarbonate, sodium dihydrogenphosphate, sodium tricitrate and disodiumhydrogenphosphate, or small amounts of siccatives or, if they arepresent in a liquid, aqueous solution (including the presence ofthickeners of the type customary in print pastes), they may also includesubstances which ensure a long life for these preparations, for examplemold preventatives.

The reactive dyes of the general formula (1) according to the inventionare preferably present as a dye powder or as a granular dye containing10 to 80% by weight, based on the powder or granules, of an electrolytesalt which is also known as a standardizing agent. Granules inparticular have particle sizes of 50 to 500 μm. These solid preparationscan further contain the aforementioned buffer substances in a totalamount of up to 10% by weight, based on the preparation. When the dyesare present in aqueous solution, the total dye content in these aqueoussolutions will be up to about 50% by weight, for example between 5 and50% by weight, and the electrolyte salt content in these aqueoussolutions will preferably be below 10% by weight, based on the aqueoussolution. The aqueous solutions (liquid preparations) can contain theaforementioned buffer substances generally in an amount of up to 10% byweight, preferably up to 2% by weight.

Reactive dyes of the general formula (1) according to the invention mayhave the same chromophor but differ with regard to the fiber-reactivegroup R². More particularly, in the case of the same chromophor, R² canbe firstly —SO₂CH═CH₂ and secondly —SO₂CH₂CH₂Z, particularly preferablyβ-sulfatoethylsulfonyl. The fraction of dye in the vinylsulfonyl formcan be up to about 30 mol %, based on the respective dye chromophor.Preferably, the fraction of vinylsulfonyl dye to β-ethyl-substituted dyeis in a molar ratio between 5:95 and 30:70.

The present invention further provides processes for preparing thereactive dyes of the general formula (1).

These are obtainable for example when a compound of the general formula(3)

where X¹, X², M and n are each as defined above, is diazotized andreacted with a compound of the formula (4)

Alternatively, a compound of the general formula (5)

where R, M, m and n are each as defined above, can be condensed with ahalotriazine of the general formula (6)

where X¹ and X² are each as defined above and X³ is fluorine orchlorine.

The compound of the general formula (6) can in turn be obtained fromtrifluorotriazine or trichlorotriazine and one or two compounds of thegeneral formula (2′)

The compounds of the general formula (1), in which X² is a radical ofthe general formula (2), are alternatively also preparable by reactionof a compound of the general formula (5) with trihalotriazine andsubsequent condensation with an amine of the general formula (2′).

Dyes of the general formula (1) where X¹ is X² and is not halogen areobtained by condensation of dyes of the general formula (1) where X¹ ishalogen by reaction with a reactive amine of the general formula (2′) inaqueous solution.

The compounds of the general formula (3) are obtainable in various ways.When X² is a radical of the formula (2), the condensation products areobtained by reaction of halotriazines (6) with diaminobenzenesulfonicacids or diaminobenzenedisulfonic acids, preferably1,3-diaminobenzene-4-sulfonic acid, 1,4-diaminobenzene-2-sulfonic acidand also 1,4-diaminobenzene-2,5-disulfonic acid and2,4-diaminobenzene-1,5-disulfonic acid, or by condensation of atrichloro- or trifluorotriazine with diaminobenzenesulfonic acids ordiaminobenzenedisulfonic acids and subsequent condensation with an amineof the general formula (2′).

The abovementioned diazotization, coupling and condensation reactionsare known per se to one skilled in the art and can be carried out in thegenerally customary manner extensively described in the field'sliterature.

The dyes of the general formula (1) according to the invention areobtained as a solution or suspension in the above-described methods ofmaking and can be isolated by salting out. They can also be spray dried;another possibility is to evaporate the solution or suspension.

The reactive dyes of the general formula (1) according to the inventionpossess useful application properties. They are used for dyeing andprinting hydroxyl- and/or carboxamido-containing materials, for examplein the form of sheetlike structures, such as paper and leather, or offilms, of polyamide for example, or in bulk, as for example polyamideand polyurethane, but especially in the form of fibers of the materialsmentioned. Preferably, they are used for dyeing and printing cellulosicfiber materials of any kind. They are also useful for dyeing andprinting hydroxyl-containing fibers present in blend fabrics, forexample blends of cotton with polyester fibers or polyamide fibers. Itis also possible to use them to print textiles or paper by the inkjetprocess.

The present invention accordingly also provides for the use of thereactive dyes of the general formula (1) according to the invention fordyeing and printing the materials mentioned or, to be more precise,processes for dyeing or printing such materials in a conventional mannerby using one or more reactive dyes of the general formula (1) accordingto the invention as a colorant.

Advantageously, the as-synthesized solutions of the reactive dyes of thegeneral formula (1) according to the invention can be used directly as aliquid preparation for dyeing, if appropriate after addition of a buffersubstance and similarly if appropriate after concentrating or diluting.

The materials mentioned are preferably used in the form of fibermaterials, especially in the form of textile fibers, such as wovens oryarns, as in the form of hanks or wound packages.

Hydroxyl-containing materials are those of natural or synthetic origin,for example cellulose fiber materials or regenerated products thereofand polyvinyl alcohols. Cellulose fiber materials are preferably cotton,but also other vegetable fibers, such as linen, hemp, jute and ramiefibers. Regenerated cellulose fibers are for example staple viscose andfilament viscose.

Carboxamido-containing materials are for example synthetic and naturalpolyamides and polyurethanes, especially in the form of fibers, forexample wool and other animal hairs, silk, leather, nylon-6,6, nylon-6,nylon-11 and nylon-4.

The reactive dyes of the general formula (1) according to the inventioncan be applied to and fixed on the substrates mentioned, especially thefiber materials mentioned, by the application techniques known forwater-soluble dyes and especially by the application techniques knownfor fiber-reactive dyes. Applied in this way by exhaust dyeing processesto cellulose fibers from a long liquor using a variety of acid-bindingagents with or without neutral salts, such as sodium chloride or sodiumsulfate, they produce dyeings having very good color yields. They arepreferably applied in an aqueous bath at temperatures between 40 and105° C., if appropriate at a temperature of up to 130° C. underpressure, and if appropriate in the presence of customary dyeingassistants. One possible procedure in this context is to introduce thematerial into the warm bath and to gradually heat the bath to thedesired dyeing temperature and to complete the dyeing operation at thattemperature. The neutral salts which speed the exhaustion of the dyesmay also, if appropriate, not be added to the bath until the actualdyeing temperature has been reached.

The padding process likewise provides excellent color yields and verygood color build-up on cellulose fibers, the dyes being fixable in aconventional manner by batching at room temperature or elevatedtemperature, for example at up to about 60° C., by steaming or using dryheat.

Similarly, the customary printing processes for cellulose fibers, whichcan be carried out either single-phase, for example by printing with aprint paste comprising sodium bicarbonate or some other acid-bindingagent and by subsequent steaming at 100 to 103° C., or two-phase, forexample by printing with a neutral or weakly acidic print color andsubsequent fixation either by passing the printed material through a hotelectrolyte-containing alkaline bath or by overpadding with an alkalineelectrolyte-containing padding liquor with subsequent batching orsteaming or dry heat treatment of the alkali-overpadded material,produce strong prints having well-defined contours and a clear whiteground. The outcome of the prints is substantially unaffected byvariations in the fixing conditions.

When fixing by means of dry heat in accordance with the customarythermofix processes, hot air from 120 to 200° C. is used. In addition tothe customary steam at 101 to 103° C., it is also possible to usesuperheated steam and high-pressure steam at temperatures of up to 160°C.

The acid-binding agents which effect the fixation of the dyes on thecellulose fibers include for example water-soluble basic salts of thealkali metals and likewise alkaline earth metals of inorganic or organicacids or compounds which release alkali in the heat. Especially suitableare the alkali metal hydroxides and alkali metal salts of weak to mediuminorganic or organic acids, the preferred alkali metal compounds beingthe sodium and potassium compounds. Such acid-binding agents include forexample sodium hydroxide, potassium hydroxide, sodium carbonate, sodiumbicarbonate, potassium carbonate, sodium formate, sodiumdihydrogenphosphate, disodium hydrogenphosphate, sodiumtrichloroacetate, sodium silicate or trisodium phosphate.

The reactive dyes of the general formula (1) according to the inventionare notable for high reactivity, good fixability, very good build-up andalso high light and perspiration-light fastness. They can therefore beused by the exhaust dyeing process at low dyeing temperatures andrequire only short steaming times in pad-steam processes. The degrees offixation are high, and the unfixed portions are readily washed off, thedifference between the degree of exhaustion and the degree of fixationbeing remarkably small, ie the hydrolysis loss being very small. Theyare also particularly useful for printing, especially on cotton, butalso for printing nitrogenous fibers, for example wool or silk or blendfabrics containing wool or silk.

The reactive dyes of the general formula (1) according to the inventionare further notable for the fact that, following the dyeing operation,unfixed dye portions are very readily washed off the fiber materialwithout adjacent whites in the washing operation being tainted by thedye which becomes detached. This is advantageous for the dye operationin that washing cycles and hence costs are saved.

The dyeings and prints prepared with the reactive dyes of the generalformula (1) according to the invention, especially on cellulose fibermaterials, possess high color strength and high fiber-dye bond stabilitynot only in the acidic but also in the alkaline range as well as goodlightfastness and very good wetfastness properties, such as washing,water, seawater, crossdyeing and perspiration fastnesses, and also goodfastness to dry heat setting and pleating and to crocking.

The examples hereinbelow serve to illustrate the invention. The partsand percentages are by weight, unless otherwise stated. Parts by weightrelate to parts by volume as the kilogram relates to the liter.

The compounds described in the examples in terms of formulae areindicated in the form of the free acid. But generally they are preparedand isolated in the form of the alkali metal salts, such as lithium,sodium or potassium salts, and used for dyeing in the form of theirsalts. Similarly, the starting compounds and components indicated in theform of the free acid in the subsequent examples, especially tableexamples, can be used in the synthesis as such or in the form of theirsalts, preferably alkali metal salts.

The absorption maxima (λ_(max)) in the visible range reported for thedyes according to the invention were determined on aqueous solutions oftheir alkali metal salts.

EXAMPLE 1

18.4 parts of 2,4,6-trichloro-1,3,5-triazine are suspended in 200 partsof ice-water at 0-5° C. in the course of 30 minutes. 30.9 parts of2-(anilino)ethyl 2-sulfatoethyl sulfone are then added over 30 minuteswhile the reaction solution is maintained at pH 2.5 by concurrentmetered addition of 15% sodium carbonate solution. The reaction mixtureis subsequently stirred at 0-5° C., then mixed with 26.8 parts of1,4-diaminobenzene-2,5-disulfonic acid and adjusted to pH 5.5 with 15%sodium carbonate solution. The reaction mixture is subsequently warmedto 35° C. and subsequently stirred for 30 minutes. It is cooled to 10°C., admixed with 6.9 parts of sodium nitrite and added dropwise to aninitial charge of 100 parts of ice and 40 parts of conc. hydrochloricacid (31%). After stirring for 1 hour, excess nitrite is removed byaddition of sulfamic acid.

23.9 parts of 7-amino-1-hydroxynaphthalene-3-sulfonic acid are dissolvedin 300 parts of water and neutralized by addition of aqueous sodiumhydroxide solution. The neutral solution is added dropwise to the colddiazotization batch at 10° C. over 30 minutes. The resulting pH is1.5-2.0. The pH is adjusted to 2.5 with 15% sodium carbonate solutionover 30 minutes and the solution is subsequently stirred at risingtemperature for 3 hours. It is then adjusted to pH 6 with sodiumcarbonate solution and buffered with NaH₂PO4/Na₂HPO₄. The solutionobtained is evaporated.

The dye obtained has the formula

It dyes and prints cotton in bluish red shades having good fastnesses,especially high lightfastness.

The dyes of examples (2) to (32) were obtained in a similar manner. Tothis end, the corresponding reactive amine was reacted withtrichlorotriazine and subsequently reacted with the condensationcomponent, diazotized and coupled onto the coupling component.

Condensation Ex. Reactive amine component Coupling component Hue λmax 2) 2-(anilino)ethyl 2-sulfatoethyl sulfone1,4-diaminobenzene-2,5-disulfonic acid 7-amino-1-hydroxy- red 528naphthalene-3,6-disulfonic  3) ″ ″ 7-sulfomethylamino- red 5361-hydroxynaphthalene- 3-sulfonic acid  4) ″2,4-diaminobenzene-1,5-disulfonic acid 7-amino-1-hydroxy- red 519naphthalene-3-sulfonic acid  5) ″ ″ 7-amino-1-hydroxy- red 521naphthalene-3,6-disulfonic acid  6) ″ ″ 7-sulfomethylamino- red 5321-hydroxynaphthalene- 3-sulfonic acid  7) ″1,4-diaminobenzene-2-sulfonic acid 7-amino-1-hydroxy- red 517naphthalene-3-sulfonic acid  8) ″ ″ 7-amino-1-hydroxy- red 524naphthalene-3,6-disulfonic acid  9) ″ 1,3-diaminobenzene-4-sulfonic acid7-amino-1-hydroxy- red 510 naphthalene-3-sulfonic acid 10) ″ ″7-amino-1-hydroxy- red 514 naphthalene-3,6-disulfonic acid 11)3-(anilino)propyl 2-sulfatoethyl sulfone1,4-diaminobenzene-2,5-disulfonic acid 7-amino-1-hydroxy- red 524naphthalene-3-sulfonic acid 12) ″ ″ 7-amino-1-hydroxy- red 527naphthalene-3,6-disulfonic acid 13) ″ ″ 7-sulfomethylamino- red 5371-hydroxynaphthalene- 3-sulfonic acid 14) ″2,4-diaminobenzene-1,5-disulfonic acid 7-amino-1-hydroxy- red 519naphthalene-3-sulfonic acid 15) ″ ″ 7-amino-1-hydroxy- red 521naphthalene-3,6-disulfonic acid 16) ″ ″ 7-sulfomethylamino- red 5321-hydroxynaphthalene- 3-sulfonic acid 17) ″1,4-diaminobenzene-2-sulfonic acid 7-amino-1-hydroxy- red 518naphthalene-3-sulfonic acid 18) ″ ″ 7-amino-1-hydroxy- red 524naphthalene-3,6-disulfonic acid 19) ″ 1,3-diaminobenzene-4-sulfonic acid7-amino-1-hydroxy- red 510 naphthalene-3-sulfonic acid 20) ″ ″7-amino-1-hydroxy- red 514 naphthalene-3,6-disulfonic acid 21)2-(4-sulfophenyl-amino)ethyl 2-sulfatoethyl sulfone1,4-diaminobenzene-2,5-disulfonic acid 7-amino-1-hydroxy- red 523naphthalene-3-sulfonic acid 22) ″ ″ 7-amino-1-hydroxy- red 528naphthalene-3,6-disulfonic acid 23) ″ ″ 7-sulfomethylamino- red 5371-hydroxynaphthalene- 3-sulfonic acid 24) ″2,4-diaminobenzene-1,5-disulfonic acid 7-amino-1-hydroxy- red 518naphthalene-3-sulfonic acid 25) ″ ″ 7-amino-1-hydroxy- red 522naphthalene-3,6-disulfonic acid 26) ″ ″ 7-sulfomethylamino- red 5311-hydroxynaphthalene- 3-sulfonic acid 27) ″1,4-diaminobenzene-2-sulfonic acid 7-amino-1-hydroxy- red 517naphthalene-3-sulfonic acid 28) ″ 1,4-diaminobenzene-2-sulfonic acid7-amino-1-hydroxy- red 525 naphthalene-3,6-disulfonic acid 29) ″1,3-diaminobenzene-4-sulfonic acid 7-amino-1-hydroxy- red 511naphthalene-3-sulfonic acid 30) ″ ″ 7-amino-1-hydroxy- red 515naphthalene-3,6-disulfonic acid 31) 3-(4-sulfophenyl-amino)propyl2-sulfatoethyl sulfone 1,4-diaminobenzene-2,5-disulfonic acid7-amino-1-hydroxy- red 524 naphthalene-3-sulfonic acid 32) ″ ″7-amino-1-hydroxy- red 528 naphthalene-3,6-disulfonic acid 33) ″ ″7-sulfomethylamino- red 537 1-hydroxy-naphthalene- 3-sulfonic acid 34) ″2,4-diaminobenzene-1,5-disulfonic acid 7-amino-1-hydroxy- red 519naphthalene-3-sulfonic acid 35) ″ ″ 7-amino-1-hydroxy- red 522naphthalene-3,6-disulfonic acid 36) ″ ″ 7-sulfomethylamino- red 5321-hydroxynaphthalene- 3-sulfonic acid 37) ″1,4-diaminobenzene-2-sulfonic acid 7-amino-1-hydroxy- red 518naphthalene-3-sulfonic acid 38) ″ ″ 7-amino-1-hydroxy- red 523naphthalene-3,6-disulfonic acid 39) ″ 1,3-diaminobenzene-4-sulfonic acid7-amino-1-hydroxy- red 510 naphthalene-3-sulfonic acid 40) ″ ″7-amino-1-hydroxy- red 515 naphthalene-3,6-disulfonic acid

EXAMPLE 41

21.8 parts of 4-nitroaniline-2-sulfonic acid are suspended in 400 partsof water and neutralized with aqueous sodium hydroxide solution. 6.9parts of sodium nitrite are added, and the suspension is stirred untileverything has dissolved.

The solution is added dropwise at 0-5° C. to initially charged 100 partsof ice and 30 parts of conc. hydrochloric acid (31%) followed bystirring for 60 minutes. Excess nitrite is removed by addition ofsulfamic acid.

31.9 parts of 7-amino-1-hydroxynaphthalene-3,6-disulfonic acid aredissolved in 300 parts of water and neutralized with aqueous sodiumhydroxide solution and added dropwise to the suspension of the diazoniumsalt over 30 minutes. The reaction mixture is gradually adjusted to pH 2with sodium carbonate solution and subsequently stirred for 1 hour. Thisaffords a dye solution which in the form of the free acid contains acompound of the formula (7)

The solution of the compound (7) is adjusted to pH 8.5 with aqueoussodium hydroxide solution and heated to 70° C. A solution of 5.6 partsof NaHS in 50 parts of water is added dropwise and stirred in for 30minutes.

The compound obtained is precipitated by addition of 150 parts of sodiumchloride, filtered off and washed with aqueous sodium chloride solution.The compound obtained conforms in the form of its free acid to theformula (8)

51.9 parts of compound (8) are dissolved in 500 parts of water. 18.4parts of 2,4,6-trichloro-1,3,5-triazine are suspended in 200 parts ofice-water at 0-5° C. in the course of 30 minutes. 30.9 parts of2-(anilino)ethyl 2-sulfatoethyl sulfone are then added over 30 minuteswhile the reaction solution is maintained at pH 2.5 by concurrentmetered addition of 15% sodium carbonate solution. The reaction mixtureis subsequently stirred at 0-5° C. for 1 hour, and the suspensionobtained is added to the solution of compound (8). The reaction mixtureis adjusted to pH 6 with sodium carbonate solution and warmed to 35° C.It is subsequently stirred for 1 hour. The end point of the reaction isdetermined by thin layer chromatography. The dye of example 6 isprecipitated by addition of potassium chloride, filtered off and dried.

The dye dyes cotton in a bluish red shade.

The compounds of examples 5), 13) and 14) are preparable in a similarmanner by condensing compound (8) with appropriate triazine derivatives.

By varying the coupling component in compound (8), it is possible toprepare compounds of the general formula (5) by the above-describedmethod. These compounds can be converted into dyes of the generalformula (1) by reaction with appropriate triazine derivatives.

Example 42

51.9 parts of compound (12) are dissolved in 500 parts of water, admixedwith 4.2 parts of sodium fluoride and cooled to 5° C. 13.5 parts of2,4,6-trifluorotriazine are then added. The pH initially decreasesbefore it adjusts to about 4-4.5. The reaction solution is subsequentlystirred for 15 minutes.

The reaction solution is then admixed with a neutral aqueous solution of40.3 parts of 3-(4-sulfophenylamino)propyl 2-sulfatoethyl sulfone addeddropwise, allowed to warm to 25° C. and all the while maintained at a pHof 6-6.5 kept constant by addition of sodium carbonate solution.

The end point of the reaction is determined by thin layerchromatography.

The solution is evaporated to leave a dye of the formula in the form ofthe free acid (9)

The dye dyes cotton in a bluish red shade.

The compounds of examples 43) to 49) are preparable in a similar mannerby the process described above.

Coupling component in Ex. Reactive amine compound of formula (12) Hueλmax 43) 3-(4-sulfophenylamino)propyl 7-amino-1-hydroxynaphthalene- red518 2-sulfatoethyl sulfone 3-sulfonic acid 44)2-(4-sulfophenylamino)ethyl 2-sulfatoethyl sulfone7-amino-1-hydroxynaphthalene- red 525 3,6-disulfonic acid 45) ″7-amino-1-hydroxynaphthalene- red 518 3-sulfonic acid 46)2-(anilino)ethyl 2-sulfatoethyl sulfone 7-amino-1-hydroxynaphthalene-red 524 3,6-disulfonic acid 47) ″ 7-amino-1-hydroxynaphthalene- red 5193-sulfonic acid 47) 3-(anilino)propyl 2-sulfatoethyl sulfone7-amino-1-hydroxynaphthalene- red 524 3,6-disulfonic acid 48) ″7-amino-1-hydroxynaphthalene- red 518 3-sulfonic acid

EXAMPLE 49

32.3 parts of 3-(anilino)propyl 2-sulfatoethyl sulfone are dissolved in200 parts of water at pH 5 by addition of 15% sodium carbonate solutionand admixed with 4.6 parts of sodium fluoride. After cooling to 0° C.,the solution is admixed with 13.5 parts of 2,4,6-trifluorotriazine. ThepH initially decreases and then adjusts to 3.5-4.0. The reaction mixtureis subsequently stirred for 15 minutes. 18.8 parts of2,4-diaminobenzene-1,5-disulfonic acid are then added, the pH isadjusted to 5.5 with sodium carbonate solution and the solution isallowed to warm to 20-25° C. After stirring for 1 hour, 6.9 parts ofsodium nitrite are added. The solution is then transferred over 30minutes into an initial charge of 100 parts of ice and 50 parts of conc.hydrochloric acid (31%). The solution is subsequently stirred for 1hour, and excess nitrite is then removed by addition of sulfamic acid.

23.9 parts of 7-amino-1-hydroxynaphthalene-3-sulfonic acid are dissolvedin 300 parts of water at neutral pH and by addition of aqueous sodiumhydroxide solution. After heating to 50° C., 13.4 parts of the sodiumsalt of formaldehyde bisulfite are added. The solution is subsequentlystirred for 30 minutes, cooled to 20° C. and added dropwise into thecold diazo solution at 10° C. The resulting pH is 1.5-2. The pH isadjusted to 2-2.5 with sodium carbonate solution and the mixture issubsequently stirred at rising temperature for 3 h. The solution isadjusted to pH 6 with sodium carbonate solution, buffered withNaH₂PO₄/Na₂HPO₄ and evaporated. This affords a dye of the formula

The dye dyes cotton in a bluish red shade.

The dyes of examples 50) to 80), which are recited in the table whichfollows, and also the dyes of examples 42) to 48) are preparable in asimilar manner by having a reactive amine starting material condensedwith trifluorotriazine, condensed with the appropriate condensationcomponent, diazotized and coupled onto the appropriate couplingcomponent.

Condensation Ex. Reactive amine component Coupling component Hue λmax50) 3-(anilino)propyl 2-sulfatoethyl sulfone2,4-diaminobenzene-1,5-disulfonic acid 7-amino-1-hydroxy- red 518naphthalene-3-sulfonic acid 51) ″ ″ 7-amino-1-hydroxy- red 522naphthalene-3,6-disulfonic acid 52) ″ ″ 7-sulfomethylamino- red 5351-hydroxynaphthalene- 3-sulfonic acid 53) ″1,4-diaminobenzene-2,5-disulfonic acid 7-amino-1-hydroxy- red 525naphthalene-3-sulfonic acid 54) ″ ″ 7-amino-1-hydroxy- red 528naphthalene-3,6-disulfonic acid 55) ″ 1,3-diaminobenezene-4-sulfonicacid 7-amino-1-hydroxy- red 510 naphthalene-3-sulfonic acid 56) ″ ″7-amino-1-hydroxy- red 514 naphthalene-3,6-disulfonic acid 57)2-(anilino)ethyl 2-sulfatoethyl sulfone2,4-diaminobenzene-1,5-disulfonic acid 7-sulfomethylamino- red 5321-hydroxynaphthalene- 3-sulfonic acid 58) ″ ″ 7-amino-1-hydroxy- red 519naphthalene-3-sulfonic acid 59) ″ ″ 7-amino-1-hydroxy- red 523naphthalene-3,6-disulfonic acid 60) ″ 1,4-diaminobenzene-2,5-disulfonicacid 7-sulfomethylamino- red 536 1-hydroxynaphthalene-3- sulfonic acid61) ″ ″ 7-amino-1-hydroxy- red 525 naphthalene-3-sulfonic acid 62) ″ ″7-amino-1-hydroxy- red 528 naphthalene-3,6-disulfonic acid 63) ″1,3-diaminobenzene-4-sulfonic acid 7-amino-1-hydroxy- red 510naphthalene-3-sulfonic acid 64) ″ ″ 7-amino-1-hydroxy- red 514naphthalene-3,6-disulfonic acid 65) 2-(4-sulfophenyl-amino)ethyl2-sulfatoethyl sulfone 2,4-diaminobenzene-1,5-disulfonic acid7-amino-1-hydroxy- red 518 naphthalene-3-sulfonic acid 66) ″ ″7-amino-1-hydroxy- red 521 naphthalene-3,6-disulfonic acid 67) ″ ″7-sulfomethylamino- red 532 1-hydroxynaphthalene- 3-sulfonic acid 68) ″1,4-diaminobenzene-2,5-disulfonic acid 7-amino-1-hydroxy- red 524naphthalene-3-sulfonic acid 69) ″ ″ 7-amino-1-hydroxy- red 528naphthalene-3,6-disulfonic acid 70) ″ ″ 7-sulfomethylamino- red 5361-hydroxynaphthalene- 3-sulfonic acid 71) 2-(4-sulfophenyl-amino)ethyl2-sulfatoethyl sulfone 1,3-diaminobenzene-4-sulfonic acid7-amino-1-hydroxy- red 510 naphthalene-3-sulfonic acid 72) ″ ″7-amino-1-hydroxy- red 515 naphthalene-3,6-disulfonic acid 73)3-(4-sulfophenyl-amino)propyl 2-sulfatoethyl sulfone1,4-diaminobenzene-2,5-disulfonic acid 7-amino-1-hydroxy- red 524naphthalene-3-sulfonic acid 74) ″ ″ 7-amino-1-hydroxy- red 527naphthalene-3,6-disulfonic acid 75) ″ ″ 7-sulfomethylamino- red 5361-hydroxynaphthalene- 3-sulfonic acid 76) ″2,4-diaminobenzene-1,5-disulfonic acid 7-amino-1-hydroxy- red 519naphthalene-3-sulfonic acid 77) ″ ″ 7-amino-1-hydroxy- red 522naphthalene-3,6-disulfonic acid 78) ″ ″ 7-sulfomethylamino- red 5311-hydroxynaphthalene- 3-sulfonic acid 79) ″1,3-diaminobenzene-4-sulfonic acid 7-amino-1-hydroxy- red 511naphthalene-3-sulfonic acid 80) ″ ″ 7-amino-1-hydroxy- red 515naphthalene-3,6-disulfonic acid

Example 81

28.1 parts of 4-(2′-sulfatoethylsulfonyl)aniline are dissolved in 250parts of water by neutralization with 15% sodium carbonate solution.Parts of the dye of example 8) are introduced into the solution and thepH is adjusted to 5.5-6. After heating to 80° C., the pH is maintainedin the adjusted range by adding sodium carbonate solution. The course ofthe reaction is monitored by thin layer chromatography. After thereaction has ended, the dye solution is cooled down, buffered and dried.This affords a powder whose structure conforms to the formula

It dyes cotton in a bluish red shade having good fastnesses, especiallyhigh lightfastness.

Examples 82) to 88) indicated in the table which follows are obtained ina similar manner by using the dyes of the indicated examples as areactant and condensing them with a reactive amine.

Starting dye Ex. example Reactive amine Hue λmax 82)  8)4-(2′-sulfatoethylsulfonyl)-N-ethylaniline red 527 83)  3)3-(2′-sulfatoethylsulfonyl)aniline red 536 84) 40)4-(2′-sulfatoethylsulfonyl)aniline red 516 85) 26)3-(2′-sulfatoethylsulfonyl)aniline red 533 86) 17) 2-(anilino)ethyl2-sulfatoethyl sulfone red 520 87)  8) 2-(anilino)propyl 2-sulfatoethylsulfone red 528 88) 26) 4-(2′-sulfatoethylsulfonyl)aniline red 533

1. A reactive dye of the general formula (1)

where R is hydrogen, alkyl or substituted alkyl, X¹ is halogen, amino,optionally substituted amino or X², X² is a substituent of the generalformula (2)

where R¹ is substituted or unsubstituted aryl, B is alkylene which maybe interrupted by an oxygen atom, and R² is a —SO₂CH═CH₂ or —SO₂CH₂CH₂Zradical, where Z is a moiety which can be eliminated by the action ofalkali, n and m are each 0 or 1, and M is hydrogen, ammonium, an alkalimetal or the equivalent of an alkaline earth metal.
 2. A reactive dye asclaimed in claim 1, wherein n is
 1. 3. A reactive dye as claimed inclaim 1, conforming to one of the formulae (1a) to (1c):

where M, n and X¹ are each as defined in claim
 1. 4. A reactive dye asclaimed in claim 1, wherein M is hydrogen or sodium.
 5. A process forpreparing a reactive dye as claimed in claim 1, which comprisesdiazotizing and reacting a reactive amine component of the generalformula (3)

where X¹, X², M and n are each as defined in claim 1, with a compound ofthe formula (4)


6. A process for preparing a reactive dye of the general formula (I) asclaimed in claim 1, where X² is a radical of the general formula (2),which comprises reacting a compound of the general formula (5)

with a trihalotriazine and subsequent condensation with an amine of thegeneral formula (2′)


7. A process of dyeing or printing hydroxyl- and/orcarboxamido-containing material which comprises contacting the dye asclaimed in claim 1 with the material.
 8. The process as claimed in claim7, wherein the material is a fiber material.